Mixed ureas



Patented June 30, 1942 MIXED UREAS Alfred Rohm, Leverkusen I. G.-Werk, Germany,

aeslgnor to General Aniline a Film Corporaftion, New York, N. Y., a corporation of Delaware No Drawing. Application November 13, 1939, Se-

rial No. 1938 304,177. In Germany November 11, v

.4 Claims. (01. 260-506) (Granted under the provisions of March 2, 1927; 357 o. c. s)

The present invention relates to mixed ureas containing solubilizing groups and to a process or preparing the same.

In my application Ser, No. 304,176 flied November 13, 1939, entitled Urethanes, a process for the manufacture of urethanes is described. This process consists in allowing chloroformic esters of aromatic hydroxy compounds to react with the aqueous solution of an aliphatic or aromatic primary or secondary amine which contains at least one watersolubilizing group.

I have found that the urethanes .thus obtained :an be converted into water-soluble mixed ureas by allowing the said urethanes to react in aqueaus solution with primary or secondary aliphatic )1 aromatic amines which may be further substituted and which may or may not contain solu- Jilizing groups. By the new process it is possible '0 prepare a large number of hitherto unknown nixed ureas having solubilizing groups. These ireas are obtained according to the process in ery good yields. The reaction is preferably caried out in rather concentrated solution; it is nostly performed at a pH of about 7 to'8; the pH 'alue may; however, be shifted to the acid or alzaline side. The temperature may vary over wide limits. In order to use up the urethane in he reaction as completely as possible it is in nest cases expedient to employ the amine in xcess.

The water-soluble mixed ureas obtained acording to the new process are valuable interiediates for the lyestuiis per se. 1

Various methods are already known for the reparation of mixed ureas having solubilizing roups. Thus, in some cases ureas can be preared by the action of phosgene upon a mixture 1 the two amines NHLRLX and NH2.R2.Y, The reas obtained correspond to the formula:

Nrratx NH.RI.Y herein R1 and R: stand fonorganic radicals preparation of dyestuffs or are I hich are diflerent from each otherand are subituted by at least one solubilizing radical X and each. By this process only a poor yield of lixed areas is obtained, since as further reaction roducts two symmetrical-'ureas CO (NH-Ri-X) ld CO(NHR2Y): are formed and since .the implete separation of these products from the ixed urea is practically not possible in most temperatures above 100 C. thus obtained do not contain water-solubilizing sec. 14, act or cases. In the same manner and with the same disadvantages and may also be prepared according to the known process ureas which correspond to the following formula:

NRR, 1 s

in which only one amine radical contains a solubilizing group. Besides the described so-called "mixed phosgenation the preparation or these last mentioned mixed ureas is also possible by allowing the isocyanate R2 -N=C=O to react with the amine NHa-R1X. This process, however, depends on the possibility of preparing the isocyanate R2N=-C=O,-the preparation of which can only be carried out in the absence or solubilizlng groups and only, if R2 contains no or only simple substituents and then in most cases only with poor yields. I

Compared with these known processes the new process shows the advantage of yielding watersoluble mixed ureas directly with excellent re sults, by a simple reaction.

The formation of mixed ureas from urethanes of aromatic hydroxy compounds and amines is further described in the literature (Chemisches Zentralblatt 1937, II, 1538). This process, however, is carried out in the absence of solvents at and the compounds groups. This process accordingly does not present the possibility of preparing mixed ureas having 'solubilizing groups.

The following examples illustrate the invention without, however, restricting it thereto.

Example 1 16.8 gins. of 'phenyl chloroformate are added drop by 'drop to a neutral to weakly acid solution of 26.1 gins. of the sodium salt of 2-amino- 5 hydroxynaphthalene-7-sulfonic acid in 400 cc.-

thus obtained 16 gms. of 1-amino-4-acetammobenzene are added. By adding sodium carbonate and sodium phosphate the reaction of the mixture is brought to pH 7.5 and the mixture is To the paste heated for several hours to 30-410 C. Thereby the urethane dissolves, phenol is split d and 1-amino-4-acetaminobenzene disappears almost completely. By taking test portions and titrating them with sodium nitrite and hydrochloric acid the course of the reaction can be checked. The phenol is now either distilled ofi with steam having a weakly acid reaction or the mixed urea is precipitated at 50 C. in well crystallized leaflets by adding sodium chloride and filtered ed. The yield is about 90% oil the theory calculated on 2 -amino- 5 -hydroxynaphthalene- '7 -sulfonic acid. The urea corresponds in the form of its sodium salt to the following formula:

NaOaS The 2-amino-5-hydroxynaphthalene-7-su1fonic acid can be replaced by any other aromatic amine containing sulfonic or, carboxylic acid groups. The l-amino-d-acetaminobenrene can be replaced by other substitution products of aniline and also by substitution products of N-alkylanilines. v

Example 2 To a paste of 0.1 mol of Z-amino-Ei-hydroxynaphthalene-'I-sulfonic acid-o-phenylurethane in 400 cc. of water 18.7 gms. of the sodium salt of 5-amino-2-hydroxybenzoic acid are added, the

mixture is brought to pH 7.5, heated to about C. until complete dissolution has occurred and stirred for 12 hours. In order to isolate the reaction product 20% sodium chloride are added. The mixed urea of 2- amino-5-hydroxynaphthalene-7-sulfonic acid and '5-amino-2-hydroxybenzoic acid deposits as fine powder and is sucked ofi. The yield is about 92%. The urea corresponds in the form of its sodium salt to the following formula:

4o naphthalene-G-sulfonic acid-o-phenylurethane in NaOaS- NH.CO.HN 'OH COONa Also in this example instead of 2-amino-5-hydroxynaphthalene-T-sulfonic acid other amlnonaphthalene or benzene sulfonic acids and carboxylic acids or their derivatives can be used. Instead of 5-amino-2-hydroxybenzoic acid numerous amines of the benzene or naphthalene series with solubilizing groups or substitution products of these compounds may be employed.

\ Example 3 To a paste 'of 0.1 mol of 1- 0-5=hydroxy- I naphthalene-'Z-sulfonic acid-o-phenylurethane 12 aeeacaa tion. The mixed urea corresponds in the form of its sodium salt to the following toula:

nnconNONm NaOzS Instead of lfil-diaminobenzene also L i-diaminobenzene sulfonic acid or 1A=diaminobenzene carboxylic acid or other diamines may be used It is also possible to prepare first the urete of M-dia 1 1-; obenzene sulionic acid and to react this urethane with 1- o-t-hydrcmnaphthalenel-sulfonic acid to form the mixed urea.

Example 4 enact-111011 NaOa NH.C O.N

CHz.CHz.OH

The same compound is obtained from diethanol-amine-phenyl-urethane (easily obtainable from diethanol-amine in aqueous solution and phenyl chloroformate) by allowing this compound to react with 2-amino-5-hydroxynaphthalene-7-= sulfonic acid.

Example 5 To a paste of 0.1 mol of Z-amino-B-hydroxy- 400 cc. of water, 30.6 gms. of the sodium'salt of 4i-hydroxy-d'-amino-azobenzene 5 carboxylic acid are added, the mixture is brought to pH 7.2 and is heated for several hours to C. until the formation of the mixed urea is complete. After acidifying, the phenol is distilled ofi with steam and the mixed urea of 2-amino-8-hydroxynaphthalene-fi-sulfonic acid and l-hydroxy-d'- amino-azobenzene-5-carboxylic acid is isolated as crystals in a yield of 90% from weakly alkaline solution by adding sodium chloride. The mixed urea corresponds in the form of its sodium salt to the following formula:

0H mNHDQHN MN OH N80 000m Instead of i-hydroxyfi -amino-azobenzene-5- carboxylic acid other aminoazo compounds and also aminodisazo dyestuffs can be employed.

Example 6 A paste of the phenylurethane of 2-amino-= 8-hydroxynaphthalene-6-sulfonic acid prepared from 26.1 gins. of the sodium salt of 2-amino-8 hydroxynaphthalene-fi-sulfonic acid and havin a volume of 300 cc. is stirred at pH 7-8 and at C. with 15 gms. of aminoacetic acid. By adding 5 gms. of sodium phosphate and by adding drop by drop sodium carbonate solution the reaction mixture is kept at pH 7-8. when the urethane is completely dissolved the mixture is further stirred for some time at 60 C. The mixed urea of il-amino-8-hydroxynaphthalene-6- sulfonic acid and amino-acetic acid is isolated as crystalline colorless powder from acid solution smas es by adding sodium chloride in. a yield of about 90%. The urea corresponds in the form of its sodium salt to the following formula:

' naconmcmcoom Ns The same compound is obtained by the reaction of the urethane obtained in aqueous solution from aminoacetic acid and phemrl chloroformate, with the sodium salt of 2-amino-8-hydroxynaphtha- .lene-fi-sulfonic acid.

Example 7 The 4-chlorophenylurethane of 2-methylamino-5-hydroxynaphthalene-'l-sulfonic acid, obtained from 27.5 gms. of the sodium salt of 2 methlyamino-5-hydroxynaphthalene-7-sulfonic acid and 20 gms. of 4-chlorophenylchloroformate,

is dissolved in 400 cc. of water. At 70% C. and pH 7.5, 20 gms. of 4.4'-diaminodiphenyl are added to the solution, the mixture is stirred for several hours, then allowed to cool to 30 C, and the excess 4.4'-diaminodiphenyl is filtered off. By addins sodium chloride the mixed urea of 2-methylamino-5-hydroxynaphthalene-'l-sulfonic acid and 4.4'-diaminodiphenyl is separated in crystalline form in' a yield of about 90%. The urea corresponds in the form of its sodium salt to the following formula:

. v I NQQWNCQH OQNH.

. Example 8 From 17.5 gills. of the sodium salt of 5-aminoz-hydroxybenzoic acid andphenyl chloroformate the phenylurethane is prepared as a paste. To this paste 17 gms. of 1.4-diaminobenzene carboxylic acid are added, the mixtureis brought to pH 7.5 and heated to 60 C. for several hours until dissolution is complete. Now the mixture is acidified and the phenol formed is distilled off with steam. When cold the 4-hydroxy-4-amino-diphenylurea-3.3-'-dicarboxylic acid can be separated with a very good yield by adding sodium chloride. The same compound can be-obtained by the reaction of the phenyl-urethane from 3-amino-6-nitrobenzoic acid with '5-amino-2-hydroxybcnzoic acid and subsequent reduction of the nitro group.

Example 9 in the form-of its sodium salt to the following formula:

Qsmo NnconNO-NK,

By heating with dilute caustic soda lye the ester group can be saponified whereby the mixed urea of 1-amino-8 hydroxynaphthalene-3.6-disulfonic acid and 1.4-diaminobenzene is obtained.

Example 10 4.4.4 ems. of the sodium salt of 4-nitro-4'- aminostilbene-2.2'-disulfonic acid are converted into the phenylurethane and heated with 30.6

ms; of the sodium salt of 4-hydroxy-4'-aminoaz0benzene-5-carb0xylic acid to C. for several hours. When the reaction is complete, the mixed urea precipitates in a very good yield'after the addition of sodium chloride in a sodium carbonate alkaline reaction. It corresponds in the form of its sodium salt to the following formula:

Instead of nitroaminostilbenedisulfonic acid there may also be employed dehydrothiotoluidine disulfonic acid, 4-aminostilbene-4'-naphthionic acid-triazole-2.2'-disulfonic acid or any aminoazo dyestuif such as the monoazodyestuil. from diazotized o-benzenesulfonic ester of 1-amino-8- hydroxynaphthalene-3.6-disulfonic acid and 1- amino-2-methoxy-5 methylbenzene which after saponification yields the mixed urea 01' 4-hydroxy-4'-amino azobenzene 5 carboxylic acid and l-(4-amino-3'-methoxy-6'-methylbenzeneazo)-8-hydroxynaphthalene-3.6-disulfonic acid. Example 11 To apaste of 0.1 mol of 2-amino-5-hydroxynaphthalene 7 sulfonic acid-o-phenylurethane in 400 cc. of water 5 gms. (=0.046 mol) of 1.4- diaminobenzene are added and the mixture heated at pH 7.5 to -80 C. until complete dissolution is reached and the diazotization value of the solution no longer decreases. The phenol is distilled ofi with steam from the acidified solution andthe di-urea is isolated. It corresponds in the form of its sodium salt to the-following formula:

moimNaconN-Omwomqws 0.1% OH OH Instead of 1.4-diaminobenzene other diaminesand their substitution products such as ethylene diamine, 4.4'-diaminodiphenyl and others can be employed.

Mixed di-ureas of three different amines can be prepared when using for the preparation of the urethane for instance the urea of 2-amino- 5-hydroxynaphthalene-7-sulfonic acid and 1.4- diaminobenzene described in Example 3 and allowing this urethane to react with any other amine.

Example 12.

0.1 moi of the phenylurethane oi d-nitro-t'= aminostilbene-2.2'=disulronic acid is allowed to react with 0.1 mol oi Z-methyl-aminmS-hydroxm naphthalene-l-sulfonic acid in the manner described in the previous examples, the phenol is distilled ofi with steam, the nitro group is reduced to the amino group and the mmed urea is isolated. it corresponds in the term of its sodium salt to the following formula:

S OsNa NH.CO.N -SOaNa S OaNB Example 13 In a similar manner amino or alkylamino derivatives of other heterocyclic compounds with or without solubilizing groups can be converted into mixed ureas.-

Example 14 A neutral paste of 0.1 mol of the phenylurethane of Z-amino-li-hydroxynaphthalene-7=- sulfonic acid is heated together with 11.7 gms. (=0.l2 moi) of cyclohexylamine for several hours to 60 0., the phenol is distilled ofi with steam from the acidified solution and the mixed urea is isolated by'adding sodium chloride. The urea corresponds in the form of its sodium salt to the following formula C Hr-C Hr C Ha NaOaS- NH.CO.HN-CH in a similar manner other cycloaliphatic primary or secondary amines and the substitution products thereof can be converted into mixed ureas.

Example 25 A neutral paste of 0.1 mol oi the phenylurethane of 2-amino-5-hydroxynaphthalene-'lsulionic acid is heated with an aqueous solution of 4 gins. (=0.l2 mol) of hydroxylamine for sev eral hours, the phenol is distilled oil with steam tram the acidified solution and the mixed urea aaeaeaa is isolated. it corresponds in the form of its sodium salt to the following formula:

NoOzB- NEE O.HN.OH

In the same manner also the substitution prod= ucts of hydroxylamine can be converted into mixed ureas.

Example 16 A neutral paste of 0.1 mol of the phenyl= urethane of 2-amino-5-hydroxynaphthalene-7=- sulionic acid is heated with an aqueous solution of 4 gms. (=0.l2 mol) of hydrazine for several hours, the phenol is distilled off with steam from the acidified solution and the mixed urea of 2-amino-5-hydroxynaphthalene-7-sulfonic acid and hydrazine (li-hydroxy-7-sulfo-2-naphthylsemicarbazide) is isolated by adding sodium chloride. In the same way also substitution prod nets of hydrazine can be employed.

Example 17 A neutral paste of 0.1 mol of the phenylurethane of Z-amino-5-hydroxynaphthalene-l sulfonic acid is heated with 10 gms. (=0.l2 mol) piperidine for several hours to 60 C., the phenol is distilled oir" from the acidified solution with steam and the mixed urea is isolated by adding sodium chloride. The urea corresponds in the form of its sodium salt to the following formula:

CHPCHH CH2: CHr-CH:

NaOaS NH.OO.N

Also substitution products of cyclic secondary amines may be employed.

I claim:

1. Process for the preparation of mixed water= soluble ureas from urethanes of the general formula:

wherein R stands for an aromatic radical, it stands for a radical selected from the group consisting of aliphatic and aromatic radicals con taining at least one solubilizing group selected from the class consisting of sulfonic, carhoxylic and hydroxy groups, and X stands for one of the group consisting of hydrogen, alkyl and aryl,

which process consists in allowing the said urethanes to react inaqueous solution with amines selected from the group consisting of primary and secondary aliphatic and aromatic amines.

2. Process for the preparation or mixed watersoluhle ureas from urethanes of the general formula:

wherein R stands for an aromatic radical, R stands for a radical selected from the group consisting oi aliphatic and aromatic radicals containing atleast one solubilizing group selected from the class consistingof sulfonic, carboxylic and hydroxy groups, and X stands for one or the group consisting of hydrogen, alkyl and aryl, which process consists in allowing the said urethanes to react in aqueous solution at medium wherein R stands for an aromatic radical, R stands for a radical selected from the group consisting of aliphatic and aromatic radicals containingat least one solubilizing group selected trom the class consisting of sulionic, carboxylic and hydroxy groups, and X stands for one oi the group consisting of hydrogen, alkyl and aryl,

which process consists in allowing the said urethanes to react in aqueous solution at pH- values of about 7 to about 8 with amines selected iron the group consisting oi primary and secondary aliphatic and aromatic amines.

4. Process for the preparation of mixed watersolubie ureas from urethanes oi. the formula:

wherein R stands for an aromatic radical, R stands for a radical selected from the group consisting oi aliphatic and aromatic radicals containing at least one solubilizing group selected from the class consisting oi sultonic, carboxylic and hydroxy groups, and X stands for one of the group consisting of hydrogen, alkal and aryl, which process consists in allowing the said urethanes to react in aqueous solution at pH- values of about 7 to about 8 and at temperatures between about room temperature and about 80 C. with amines selected from the group consisting of primary and secondary aliphatic and aromatic amines.

ALFRED ROI-1M. 

